Acetylation of hydroxy nitriles



, that the esters through catalysts used for esteriflcation.

Patented Mar. 12, 1946 UNITED STATES" PATENT OFFICE 2.29am acnma'rron OF maoxr NITBILES Ober C.

Slotterbeck, Clark 7 Township, Union County, N. 1., assignor to Standard Oil Development Company,

a-corporation of Delaware No Drawing. Application December 28. 1943, Serial No. 515.983

9 Claims. (Cl. zen-+464) tonitrile is reacted with acetic anhydride to term lactonitrile acetate and acetic acid as follows-- CHsCH(OH) CN+ (CHsCO) 20' CHaCHiOOCCHs) CN-l-CHiCOOH This type reaction is of interest for the reason pyrolysis may be converted to the vinyl nitriles which are intermediates in synthetic rubber production. when lactonitrile acetate is heated to 400-500 C. it is converted into acrylonitrile and acetic acid. Utilizing the illustrated series of steps iactonitrile, which cannot be dehydrated directly to acrylonitrile, may be converted to vinyl nitrile. The principal diificulty with the foregoing process is that it results in the production or 2 molecules of acetic acid which must either be disposed of as a by-product or subjected to the very diflicult 3 process of reconverting the acid to acid anhydride. Direct esteriflcation oi the lactonitrile with acetic acid has been attempted. However, the water liberated during the reaction hydrolyzes the nitrile group to the corresponding acetylated amide or acid in the presence of the usual The principal object of the present invention is the development of a process for the direct esterificatlon of alpha hydroxy alkyl cyanides with organic carboxylic acids. This and other objects will be apparent to those skilled in the art upon reading the iollowing description.

It has now been found that alpha hydroxy alkyl cyanides can be reacted with organic carboxylic acid to form the alpha hydroxy alkyl cyanide esters it the reaction is conducted in the presence of an organic sulionic acid catalyst and an entrainer for removing water from the sphere of the reaction, under reflux temperature and pressure conditions to give azeotropic distillation invention have the general formula,-

ganic carboxylic acid toyield an ester.-

a preferred, for the reasons that the organic sulv aa'momcn wherein R is an alkyl radical such as.methyl, ethyl, propyl, etc. and R is hydrogen or an alkyl radical. Illustrations of these individual compounds falling within this class are lactonitrile' (alpha hydroxy ethyl cyanide) and acetone cyanohydrin (alpha hydroxy isoprcpyl cyanide).

In the present invention the hydroxy radical of the cyanohydrin compound reacts with This reaction may be illustrated by the iollowing equation-- on coca" a-c-cN HOOCB" a-c-oir 11.0

wherein R is an alkyl radical; R. and R" are hydrogen or an alkyl radical.

Suitable acids for esteriiyins the OH radical For example; m of the cyanohydrin are such esters as acetic, propicnic, benzoic, stearic, oxalic acids. The reaction is promoted by the use 01 an organic sultonic acid a the catalyst for which purpose benzene sulfonic acid and paratoluene sulionic acid are ionic acids,it has been found, promote esteriflcation while in ibiting nitrile hydrolysis.

In carrying out the reaction, the reactants are placed in the reactor equipped with a reflux condenser. To this mixture in the reaction there is then added an entraining fluid capable or forming an azeotrope with water and small amounts of catalyst. The materials are then heated slight- 1y above the boiling point of the entrainer until the reaction iscomplete as shown by the absence of water in the condensed entraining-fluid. Since the esterifying acid. water and entrainer form a ternary agent, due consideration to this fact must be given when mixing the reactants, provision being made for suflicient excess esterifying acid over and above that required for esteriiicaticn to permit the formation of the azeotropes. Generally from 1% to 2 inch: of esteriiying acid per mol 0! cyanohydrin will be found to be suilicient. A relatively inert material capable of forming an azeotrope with water, said azeotrope having a boiling point below the boiling point of either the esteriiying acid or. cyanohyfor the particular entrainer used. The alpha hydro xy alkyl cyanides or alpha hydroxy alkane 1 nitriles useful as starting materials in the present drin may be used to remove the water formed, from the sphere of the reaction. For this purpose normal propyl acetate, methyl normal propyl ketone, benzene or toluene have been found to be quite suitable, toluene being preferred. The

amount 01 entralner used is governed by the thetic rubber-like polymers.

from the waterremoved from the reaction zone.

Care must be. exercised'in the use of the catalyst, which should not exceed 0.5% 'by weight calculated on the basis of pure sulfonic acid and reactants charged to the reactor. Usually the catalyst will be present in the range from 0.1% to;

0.5% by weight with about 0.3% byweightbeing preferred. As the reaction proceeds a'conboxylic acid, selected from the group consisting stant boiling mixture of entrainer and; water or entrainer, water and esteriiying acid is taken overhead, condensed, and after' thewater; which settles as a lower layer in the condensation, is'

removed, the entrainer or entrainer and acid is returned to the reaction zone.

The results of several actualruns given in tabulated form below will serveto further illustrate the principles oi the invention.

carboxylic acid, selected from the group consisting of mono and dibasic organic carboxylic acids, in the presence of benzene sulfonic acid in an entrainer under reflux conditions, said entrainer selected from the group consisting of normal propyl acetate, methyl normal propyl ketone, benzene'and toluene.

3. A method for producing esters of alpha hydroxy alkyl cyanides which consists in reacting a hydroxy alkyl cyanide with an organic carof mono and dibasic organic carboxylic acids, in'thepresence of para toluene sulfonic acid in methyl n-propyl ketone under reflux conditions.

' said entrainer selected from the group consisting of normal propyl acetate, methyl normal propyl aketone, benzene and toluene.

4. A method for producing esters of lactonitrile ganic carboxylic acid, selected from the group consisting of mono and dibasic organic carboxylic acids, in the presence of an organic sulfonic acid TABLE I Direct esterificatzon of lactomtrile to lactonitrile :1 i acetate I Run A B 0 1' D. E F

Entrainer 1 Q) yst 96% 2 4 8 (0 2') Catalyst concentration, equivalents 0. 0263 0. 02 0. 026 0. 053 0. 0053 0. 02B

Entrainer moles l. 1. 63 1. 75 1. 75 1. 75 0. 34

Acetic acid do- 2. 02 2. 02 2. 00 2. 2. 00 4. 41

Lactonitr do 0. 695 0. 695 0. 686 0. 693 0. 692 0. 680

Reaction im f minu 399 3 450 425 3110 210 Reaction ature 110-112 110-112 110-112 110-112 110-112 112-114 Reaction products:

" Waterv overhead mole 0.638 0.333 I 0.569 0. 594 0. 461 0. 483 Acetic i I d0.';i-- 1. 1.63 .1. 395 1.375 .3. 59 Lactonitrile' acetate, moles (B. P. 78-82" C./30 mm.) 0. 547 0. 268 '0. 517 0. 556 0. 460 0.497

' Lactonitrile, moles (B. 1. 94-100" C./30 mm.) 0. 097 0:138 0. 099 0.121 0. 187 0 Polymerrams 22.6 2.0. 8.0 5 Residue do I 16. 6 8.7 24. 7 30. 7 21.2 21.8

Yield of lactonitrile acetate. mole per cent. 79 39 75. 3 80. 2 66. 5 7l. 6

Conversion of lactonitrile 0.-..- 86 85. 6 82. 5 73. 0 100 le'ctive 1 er cent.. 1 i 92 $8 88 97 01 71.6- Percentrecovery: 'Entrainer... 74. 0 92 3 90. 3 89' 95 1 geiiistilled niethyln-propyl ketone 13.1. 02-10390. j o uene. I p-Tolueue sulionic acid monohydrate.

4 Crude benzene sull'onic acid (65%) was treated with lime to destroy tree sulfuric acid.

. Includes catalyst as calcium salt, calcium acetate as polymeric material not distillable;

It should be noted from the foregoing, that sulfuric acid is not an effective catalyst for this reaction as shown by the high polymers produced as well as the low yield and lowse1ectivity...It

should also be noted as shown in therun'sthat too low a concentration of catalyst results in a low yieldeven thoughan abnormallylong reaction time is given. -..The products obtained by. the present invention can be pyrolyzed to .vinyl'type vnitriles which are useful in the production or syn Whatisclaimedis:- 1. A method for producing esters of alphahyzdroxy alkyl cyanide which consists in reacting alpha hydroxy alkyl cyanide with an organic carboxylic acid, selected from the group'consis'ting of mono and dibasic organic carboxylic'acids, in the presence of para toluene sulfonic acidinian entrainer under reflux conditions said entrainer selected from the group consisting of normal propyl acetate, methyl normal propyl keton'e, benin an entrainer under reflux conditions, said entrainer selected from the group consisting of normal propyl acetate, methyl normal propyl ketone, benzene and toluene.

5. 'A method for producing esters of lactonitrile which consists in reacting lactonitrile with an organic mono-carboxylicacid, selected from the group consisting of mono and dibaslcorganic carionic acid 1 in toluene under reflux conditions.

7:. A method forproducing lactonitrileacetate which consistsin reacting lactonitrile with. acetic 1 I acid in-the presence 'ofbenzene sulfonic acid in -mula toluene under reflux conditions.

8. A method for producingesters of alpha-hydrox'y alkyl cyanides which consists in reacting an alpha-hydroxy alkane nltrile having the form'ctomcn wherein R is an alkyl radical; R is a substituent selected from the group consisting of hydrogen atoms and alkyi radicals, with an organic carboxylic acid selected from the group consisting of mono and dibasic organic carboxyiic acids, in the presence of an aromatic sulfonic acid in an entrainer under reflux conditions, said entrainer being selected from the group consistin: of normal prowl acetate. methyl normal propyl ketonc. benzene and toluene.

9. A method for producing acetone cyanohydrin acetate which consists in reacting alpha-hydroxy isopropyl cyanide with acetic acid in the presence of benzene sulionic acid in. toluene under reflux conditions.

OBER C. snom'mnncx. 

